Substituted gamma-butyrolactones,amine derivatives thereof and organic fluids containing same

ABSTRACT

THE ALKYL GROUP BEING AS DEFINED ABOVE, X BEING OXYGEN, IMINO, ALKYLIMINO, POLYALKYLENRPOLYAMINO OR LACTAM (POLYALKYLENEPOLYAMINO) AND THE DANGLING VALENCES BEING HYDROGEN OR LOWER ALKYL (THAT IS, NO GREATER THAN 6 CARBON ATOMS).   X&lt;(-CO-C(-)(-)-CH(-)-CH(-ALKYL)-)   GAMMA-ALKYL-GAMMA-BUTYROLACTONES HAVING AN ALKYL SUBSTITUENT OF AT LEAST 16 CARBON ATOMS IN LENGTH, PREFERABLY AT LEAST 25 CARBON ATOMS, ARE FORMED BY RREACTING A MONOOLEFIN WITH A CARBOXYLIC ACID IN THE PRESENCE OF A REDUCIBLE METAL ION OF HIGHER-VALENT FORM, SUCH AS THE MANGANIC ION, MN+3. THE RESULTING LACTONES ARE USEFUL AS ANTIWEAR AGENTS AND FOR IMPROVING THE ADHERENCE OF WAX COATINGS OF PAPER AND, UPON REACTION WITH AMINES, POLYALKYLENEPOLYAMINES, FOR PROVIDING NOVEL LACTAMS AND BISLACTAMS USEFUL AS MULTIFUNCTIONAL AGENTS IN LUBRICANTS, FUELS, COOLANTS AND OTHER ORGANIC FLUIDS. THUS, THE COMPOUNDS OF THIS INVENTION ARE OF THE GENERAL STRUCTURE

United States Patent Office 3,734,865 SUBSTITUTED GAMMA-BUTYROLACTONES,

AMINE DERIVATIVES THEREOF AND OR- GANIC FLUIDS CONTAINING SAME El Ahmadi I. Heiba, Princeton, and Ralph M. Dessau,

Highland Park, N.J., assignors to Mobil Oil Corporation No Drawing. Continuation-in-part of application Ser. No.

799,939, Feb. 17, 1969, which is a continuation-inpart of abandoned application Ser. No. 714,447, Mar. 20, 1968. This application Aug. 30, 1971, Ser. No.

Int. 1g]. C10n1 1/20, ]/32 US. Cl. 25251.5 9 Claims ABSTRACT OF THE DISCLOSURE Gamma-alkyl-gamma-butyrolactones having an alkyl substituent of at least 16 carbon atoms in length, preferably at least 25 carbon atoms, are formed by reacting a monoolefin with a carboxylic acid in the presence of a reducible metal ion of higher-valent form, such as the manganic ion, Mn+ The resulting lactones are useful as anti- 'wear agents and for improving the adherence of wax coatings of paper and, upon reaction with amines, polyalkylenepolyamines, for providing novel lactams and bislactams useful as multifunctional agents in lubricants, fuels, coolants and other organic fluids. Thus, the compounds of this invention are of the general structure H a1k 1- |3o11 the alkyl group being as defined above, X being oxygen, imino, alkylimino, polyalkylenepolyamino or lactam (polyalkylenepolyamino) and the dangling valences being hydrogen or lower alkyl (that is, no greater than 6 carbon atoms).

CROSS-REFERENCE TO RELATED APPLICATIONS This application is a continuation-in-part of application Ser. No. 799,939, filed on Feb. 17, 1969, now abandoned which is a continuation-in-part of application Ser. No. 714,447, filed Mar. 20, 1968, now abandoned.

BACKGROUND OF THE INVENTION Field of the invention This invention relates to novel gamma-substituted gamma-butyrolactones, and in particular it relates to gammaalkyl lactams having at least 16 carbon atoms in the alkyl substituent and to amine derivatives thereof.

Description of the prior art In US. Pat. No. 2,296,709 of Fernholz there is disclosed gamma-butyrolactones made by the oxidation of alpha-tocopherol, not be the reaction of an olefin with a carboxylic acid. In US. 3,200,075 of Anderson and 3,261,- 782 of Anderson et al., the lactones disclosed contain an amido or a carboxyl substituent on the ring adjacent to the carbonyl carbon atom. The substituent attached to the carbon atom adjacent to the ring oxygen may contain from 1 to 300 carbon atoms. In US. 3,487,452 of Wygant et al., the lactones disclosed also contain the alpha-amido substituent and an alkyl substituent of up to 20 carbon atoms. These patents fail to disclose specific gamma-alkylsubstituted butyrolactones derived from olefins having a a chain length of at least 16 carbon atoms and carboxylic acids, or their alkylenepolyamine derivatives or the utility of the lactones as a wax coating adherent or the utility of 3,734,865 Patented May 22, 1973 the lactones or the amine derivatives as multifunctional agents in industrial organic fluids.

SUMMARY OF THE INVENTION In accordance with the present invention, there are provided novel substituted gamma-butyrolactones and gamma-butyrolactams having the formula wherein X is oxygen, imino, alkylimino, or an irnino linkage derived from a polyalkylenepolyamine or a lactam (polyalkylenepolyamine); wherein R and R are individually hydrogen or alkyl of from 1 to 5 carbon atoms, and each may be the same or different; R" is hydrogen or alkyl of 1 to 3 carbon atoms; and R" is an alkyl group containing at least 16 carbon atoms in length, preferably a total of at least 25, and more preferably from 25 to about carbon atoms. When X is an imino, the compound is a lactam or a bis-lactam. Preferably, X is derived from a polyalkylenepolyamine:

wherein n is an integer of 2 to 4 and m is an integer of 1 to. 10.

DESCRIPTION OF SPECIFIC EMBODIMENTS The lactones represented by the general formula shown above can be prepared by the process described in application .Ser. No. 714,447 now abandoned in favor of continuation-in-part application Ser. No. 799,939. The olefinic reactant is a 1- to 4- monoolefin having at least 16 carbon atoms in a straight chain and preferably at a total of 25 to 100 carbon atoms per molecule.

Typical of such olefins are: l-hexadecene, 1-heptadecene, l-octadecene, l-eicosene, l-pentacosene; l-hexacosene, l-heptacosene; l-octacosene; l-triacontene and polymers of short chain olefins such as ethylene, propylene, butene and isobutene having molecular weights of up to 5000. One such advantageous olefin is a C terminal monoolefin having a melting point of 30-40 C. Internal monoolefins may also be used, but preferably no higher than 2-olefin and 3-olefin types.

With respect to the carboxylic acid used in preparing the lactams of this invention, suitable reactants include acetic, propionic, butyric, pentanoic, hexanoic and heptanoic acids and their isomers. Acetic acid is the preferred reactant.

A preferred method of producing the latter is from a carboxylic acid solution of the metal ion, e.g. an acetic acid solution of manganic acetate. The solution is heated to temperatures up to the boiling point, or even above the boiling point when pressure is used. It is understood that a transient free radical is probably generated via hydrogen loss from a molecule of the acid which acts as a ligand to Mn.

Other useful methods for producing carboxymethyl free radicals are described in application Ser. No. 714,447.

Other free radicals, corresponding to the formula,

o-oootr,

may be generated from manganic ions and an acid, e.g. propionic, butanoic, pentanoic and the like. In each case, the acid has at least one alpha hydrogen atom. With propionic acid, the free radical is methylcarboxymethyl, CH CHCOOH; with butanoic acid, it is ethylcarboxymethyl, CH CH CHCOOH; and with methylpropionic acid it is dimethylcarboxymethyl, CH (CH )CCOOH. In the foregoing free radical preparations, the manganic salts could include propionate, butyrate, isobutyrate and hexanoate (caproate).

The preferred metal ion for use in the process for forming the lactones is trivalent manganese, or manganic ion, Mn, which is reducible to bivalent manganese or manganous ion, Mn. Manganic acetate dihydrate is a preferred Mn+ -producing compound. Cerium is also a useful metal in this invention.

The solvent for the reactiing monoolefin and the manganese compound, or other metal compound, is preferably an alpha-hydrogen-containing aliphatic carboxylic acid, in excess quantities of the acid used in the reaction is satisfactory. As stated, acetic acid is the preferred reactant-solvent. Other suitable solvents and details in the process for forming the lactones are made available in said abandoned application Ser. No. 714,447.

As theorized, the olefin is simply admixed with the metal carboxylate in the presence of excess carboxylic acid and the temperature is increased to 150 to 250 C. The following simplified sequence is understood to occur:

If the olefin is a terminal olefin (R"=hydrogen) only the gamma carbon is substituted. When acetic acid is used (R and R=hydrogen) there is no alpha substitution. Straight chain acids of 3 or more carbon atoms furnish mono-alpha substitution; 2,2-disubstituted acids result in di-alpha substitution. R contains at least 16 carbon atoms in length, and preferably has a total carbon atom content of at least 25. Excess branching is undesirable for reasons of solubility, performance and ease of biodegradability which may be important under certain uses.

The lactones so produced have utility in increasing the adherent properties of wax to paper by hot melt technique. Moreover, in hydrocarbon fluid, they provide unexpected antiwear properties.

Upon reaction of the lactones of this invention with tetraethylene pentamine and similar polyalkylene polyamines of the formula H N(C,,H ,,NH) H, wherein n is an integer of 2 to 4 and m is an integer of from 1 to 10, and the removal of water, lactams or bislactams may be produced. Reaction with the amine is believed to open the lactone ring. However, the removal of water closes the ring again wherein the cyclic oxygen atom has been replaced by the basic nitrogen atom of amine. Accordingly, reactions of 1:1 to 2:1 oflactone to amine provide useful longchain lactam and bislactam products useful in organic fluids as detergents and antioxidants. Ethylenepolyamines are preferred.

For the purpose of providing such additive properties, it has been found that polymeric olefins of propylene and butene and the like are most suitable. Polyolefins of molecular weights ranging up to 5000 may be used, and preferably up to about 2000 (about 140 carbon atoms).

The lactones may also be reacted with mono-amines to provide useful products. For example, a butene or isobutene polymer containing about carbon atoms and having terminal unsaturation is reacted with manganic acetate to form the lactone.

CEE$HCH2,

C II 0 then reacting this with an amine, R NH to form products like By further treatment of (I) with an amine, R,,NH;,, there may be formed Compounds (II) and (III) are also useful as antioxidants. R,, is alkyl or aryl of from 1 to about 20 carbon atoms.

The following examples serve to illustrate and in no sense limit the invention. All parts are by weight unless otherwise specified.

(A) PREPARATION OF LACTONES Example 1 A four-neck, five liter flask equipped with a stirrer, thermometer, N inlet and a condenser, is charged with 2800 grams of glacial acetic acid and 1200 grams of potassium acetate. The resulting mixture is heated to reflux. A quantity, 210 grams or approximately 0.5 mole, of the C terminal olefin described above, and 283.5 grams of manganic acetate dihydrate are added to the mixture. After one hour of heating at reflux, a clear solution is obtained. An additional 283.5 grams of the manganic acetate is added, and refluxing is continued for an additional hour, whereupon a clear solution is obtained. The solution is cooled to about 20 C. and is diluted with 5 volumes of water. A waxy layer containing the lactone product forms on top of an aqueous layer and is decanted.

Ethanol (1000 ml.) and 50 grams of potassium hydroxide dissolved in 400 ml. of water are added to the waxy layer, whereupon the potassium salt of the lactone is formed. The reaction mixture is refluxed for one hour. An additional liter of water is added to the mixture, which is then extracted with carbon tetrachloride (1000 ml.) to remove unreacted olefin. The aqueous layer and CC], layer which are formed are separated. The aqueous layer is acidified with HCl (12 N, ml.), whereupon the lactone is reformed. The acidified layer is extracted with toluene (500 ml.). An aqueous layer and a toluene layer which are formed are separated. The toluene layer is distilled to remove solvents and water, and is concentrated on a rotovac. A light brown product (115.6 grams) is recovered. Infrared analysis reveals 8 percent of olefin present in the product, and vapor phase chromatography indicates a 7% olefin content. The melting point of the product is 35- 50 C.

Example 2 Using similar equipment and procedure as that of Example 1, l-octadecene is reacted with manganic acetate dihydrate in the presence of excess acetic acid. The resulting reaction mixture is separated as in Example 1 in which the organic phase contains gamma-hexadecyl-gammabutyrolactone.

Example 3 Using equipment and reaction conditions similar to that of Example 1, a l-polybutene having a molecular weight of about 830 is reacted with manganic acetate in the presence of acetic acid. The reaction product is separated in the 5 same manner as in Example 1 except potassium hydroxide is not used. The organic phase is separated from the aqueous phase by use of water washes and interfacial separation. The organic phase contains the corresponding gamma-polybutenyl-gamma-butyrolactone.

Example 4 Using conditions similar to that of Example 3, a 1- polybutene of molecular weight of about 1380 is reacted with manganic acetate in the presence of acetic acid. After water washes and separations, the final organic phase contains the corresponding gamma-polybutenyl-gamma-butyrolactone.

(B) REACTION OF LACTONES WITH AMINES Example In a reaction vessel filled with a nitrogen inlet and thermometer, 62.1 grams (0.2 mole) of the lactone prepared in accordance with Example 2 is mixed with 18.9 grams (0.1 mole) of tetraethylenepentamine (for bislactams: 2:1 of lactone to amine). The reaction mixture is heated at 250 F. for 2 days under agitation with periodic nitrogen sweep to remove water vapor. Infrared tracking shows disappearance of the lactone absorption at 5.65 microns and appearance of the lactam absorption at about 6.1 microns. The viscous reaction mixture is mixed with hexane and activated charcoal; the charcoal is filtered out and the hexane removed by stripping under vacuum. The resulting product contains C mHsa C ioHaa N-(CHzCI-ENH) aCHzCHzN Example 7 The lactone of Example 4 and triethylenetetramine are reacted in a manner similar to that of Example 6. The reaction product contains (polybutenyl, MW1350) (polybutenyl, MW1350) EVALUATION OF PRODUCTS (1) Antiwear tests Three 52-100 steel half-inch diameter balls are held immovable in a ball cup. A fourth ball attached to a rotatable spindle is brought into contact with the three at a force of kg. and rotated against them at a speed of 600 rpm.

or 23.3 cm./second, for 30 minutes. The lubricant for the rotation is cetane containing 0.1% by weight of a lactone. The ball cup and lubricant is held at 200 F. during the test. This four-ball test is a known procedure described in U.S. Pat. No. 3,278,432. The lubricant rating is based on the diameter of the weld scar (WSD) on the balls (in mm.) and the wear rate (in cc./cm. 10"). The lactones of Examples 1 and 2 are evaluated in this test since they are the only additives in the lubricant fluid. Other lactones of lower carbon-atom normal olefins are also tested; the heading R indicates the number of carbon atoms or, if none, hydrogen, in the gamma position. The results are:

The reduced wear of the steel in the last two results indicate the unexpected properties of the long chain gammasubstituted-gamma lactones of this invention.

The lactone of Example 2 is reacted with triethylenetetramine in the same manner as in Example 5. The bislactam product is added to a kerosene jet fuel, JP7 which meets U .8. Mil. Spec. MIL-T-38219, at a concentration of 50 ppm. This composition is submitted to the pinon-disk wear test described in detail in U.S. No. 3,554,908. In this test, the force is 4 kg,; the apparatus is run at 46 cm./second at F. for 3 hours. The same ratings as in the previous four-ball test are used. The jet fuel is also tested without additive. The results are:

(2) Antioxidant tests In this series of tests, a solvent refined mineral oil of 100 SUS at 100 F. and 0 F. pour point, containing 1% by weight of the bis-lactams of this invention, is subjected to oxidation at C. by the following procedure: Into a vessel containing 30 grams of the oil composition oxygen is circulated at 5 liters per hour through a solenoid valve, in which the rate of oxygen absorption is measured. The time in hours which 1 mole of oxygen per kilogram of oil is absorbed by the oil is obtained; the longer the time the more resistant the oil composition. Also measured is the amount in grams of deposit caused by the oxidation during the oxidation period; the deposit is washed in hex ane before being Weighed. A test similar to that used here is described in U.S. No. 3,554,945. The bislactams tested are the products of Examples 5, 6 and 7. As a comparison the oil alone and the bis-lactam of gamma-octyl-gammabutyrolactone and triethylenetetramine are tested. The results are:

Absorption Additive time, hrs. Deposit, grams None 20. 0 0. 234 Ootyl-group- 28. 6 0. 4258 Example 5 40. 1 0. 4493 Example 6. 40. 4 0.2755 Example 7 35. 6 0.3813

A mixture of 0.5% by weight of the product of Example and 0.5% by weight of the said succinimide in the same oil is tested in the oxidation test. The unit absorption time is 42.6 hours.

It will be seen that the lactones and their amine derivatives in accordance with this invention are useful agents in industrial organic fluids such as lubricants, fuels, greases and the like. They may be used alone or in conjunction with other additives, such as the polyalkenylsuccinimides.

Mixed lactones of various alkyl carbon atom lengths may also be used, as shown in Example 8.

Example 8 A mixture of C to C l-olefins is reacted with manganic acetate in the presence of acetic acid as described in Example 1, except that the manganic acetate is prepared in situ by adding potassium permanganate in sufficient amount to produce conversion to the higher oxidation level. The average chain length of the olefin is about 17. The resulting lactone product is separated and 118.6 grams is mixed with 35.1 grams of triethylenetetramine in a manner similar to Example 5. Some water is distilled off to permit the temperature to reach 250 F.

Aspects of this invention have been described in narrow terms, however all modifications thereof which would be obvious are considered to be within the scope of this invention, as claimed in the following claims.

What is claimed is:

1. A composition comprising an organic fluid selected from the group consisting of a lubricating oil and a hydrocarbon fuel in major amount and, in amount sufiicient to provide antiwear, detergent or antioxidant properties thereto, the compound having the formula wherein the alkyl group has at least 16 carbon atoms, the dangling valences are individually selected from the group consisting of hydrogen and lower alkyl, X is selected from the group consisting of oxygen,

wherein n is an integer of 2 to 4 and m is an integer of and R and R are individually selected from the group consisting of hydrogen and alkyl of from 1 to 5 carbon atoms, R" is selected from the group consisting of hydrogen and alkyl of from 1 to 3 carbon atoms, and R is alkyl having a chain length of at least 16 carbon atoms.

5. The composition of claim 4 wherein the compound has the structure 6. The composition of claim 4 wherein R contains from 25 to carbon atoms.

7. The composition of claim 4 wherein R, R and R" are hydrogen.

8. The composition of claim 4 wherein R is alkyl having a total of at least 25 carbon atoms.

9. The composition of claim 4 wherein R is alkyl having a total of from 25 to carbon atoms.

References Cited UNITED STATES PATENTS 1/1967 Anderson 252-51.5 R 7/1960 Buc et a1 252--51.5 A

DANIEL E. WYMAN, Primary Examiner W. H. CANNON, Assistant Examiner US. Cl. X.R.

25252, 51.5 R; 44-63; 260-3263, 326.5 FL, 343.6 

